Multifunctional electrode

ABSTRACT

A nonvolatile memory element is disclosed comprising a first electrode, a near-stoichiometric metal oxide memory layer having bistable resistance, and a second electrode in contact with the near-stoichiometric metal oxide memory layer. At least one electrode is a resistive electrode comprising a sub-stoichiometric transition metal nitride or oxynitride, and has a resistivity between 0.1 and 10 Ωcm. The resistive electrode provides the functionality of an embedded current-limiting resistor and also serves as a source and sink of oxygen vacancies for setting and resetting the resistance state of the metal oxide layer. Novel fabrication methods for the second electrode are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation claiming priority to U.S. Pat. App.Ser. No. 14/017,942 filed 4 Sep. 2013, itself a continuation claimingpriority to U.S. patent application Ser. No. 13/367,662 filed 7 Feb.2012, each of which is entirely incorporated by reference herein for allpurposes.

FIELD OF THE INVENTION

One or more embodiments of the present invention relate to ReRAM devicesand methods of making ReRAM devices, and more particularly to methodsfor forming electrodes having embedded resistor functionality.

BACKGROUND

Nonvolatile memory elements are used in systems in which persistentstorage is required. For example, digital cameras use nonvolatile memorycards to store images and digital music players use nonvolatile memoryto store audio data. Nonvolatile memory is also used to persistentlystore data in computer environments.

Nonvolatile memory is often formed using electrically-erasableprogrammable read only memory (EEPROM) technology. This type ofnonvolatile memory contains floating gate transistors that can beselectively programmed or erased by application of suitable voltages totheir terminals.

As fabrication techniques improve, it is becoming possible to fabricatenonvolatile memory elements with increasingly smaller dimensions.However, as device dimensions shrink, scaling issues are posingchallenges for traditional nonvolatile memory technology. This has ledto the investigation of alternative nonvolatile memory technologies,including resistive switching nonvolatile memory known in array form asresistive random access memory or ReRAM.

Resistive switching nonvolatile memory is formed using memory elementsthat have two or more stable states with different resistances. Bistablememory has two stable states. A bistable memory element can be placed ina high resistance state or a low resistance state by application ofsuitable voltages or currents. Voltage pulses are typically used toswitch the memory element from one resistance state to the other.Nondestructive read operations can be performed to ascertain the valueof a data bit that is stored in a memory cell.

Resistive switching based on transition metal oxide switching elementsformed of metal oxide layers has been demonstrated. Although metal oxidelayers such as these exhibit bistability, the resistance of these layersand/or the ratio of the high-to-low resistance states is (are) ofteninsufficient to be of use within a practical nonvolatile memory device.For instance, the resistance states of the metal oxide layer shouldpreferably be significant as compared to that of the system (e.g., thememory device and associated circuitry) so that any change in theresistance state change is perceptible. Since the variation in thedifference in the resistive states is related to the resistance of theresistive switching layer, it is often hard to use a low resistancemetal oxide layer to form a reliable nonvolatile memory device. Forexample, in a nonvolatile memory that has conductive lines formed of arelatively high resistance metal such as tungsten, the resistance of theconductive lines may overwhelm the resistance of the metal oxideresistive switching element if its resistance was not sufficiently high.It may be difficult or impossible to sense the state of the bistablemetal oxide resistive switching element.

Similar issues can arise from integration of the resistive switchingmemory element with current steering elements, such as diodes ortransistors. The resistance of the resistive switching memory element(at least in its high resistance state) is preferably significantcompared to the resistance of the current steering elements, so that theunvarying resistance of the current steering element does not dominatethe resistance of the switching memory element, and thus reduce themeasurable difference between the “on” and “off” states of the formedmemory device (i.e., logic states of the device). However, since thepower that can be delivered to a circuit containing a series ofresistive switching memory elements and current steering elements istypically limited in most conventional nonvolatile memory devices (e.g.,CMOS driven devices), it is desirable to form each of the resistiveswitching memory elements and current steering elements in the circuitso that the voltage drop across each of these elements is small, andthus resistance of the series connected elements does not cause thecurrent to decrease to an undesirable level due to the fixed appliedvoltage (e.g., ˜2-5 V).

As nonvolatile memory device sizes shrink, it is important to reduce therequired currents and voltages that are necessary to reliably set, resetand/or determine the desired “on” and “off” states of the device tominimize overall power consumption of the memory chip as well asresistive heating of the device and cross-talk between adjacent devices.Moreover, as nonvolatile memory device sizes shrink it becomesincreasing necessary to assure that the “set” and “reset” currents usedto change the state of the memory element are not too large so as torequire higher voltage transistors for chip control circuitry, as wellto minimize damage to or alter the electrical or physical properties ofthe one or more layers found in the formed memory device. A largecurrent flowing through the current carrying lines in a memory array canalso undesirably alter or disturb the memory state of otherinterconnected devices or possibly damage portions of the adjacentlyconnected devices, due to an appreciable amount of “cross-talk” createdbetween them due to resistive heat transfer. Therefore, there is a needto limit and/or minimize the required current used to sense and programthe logic states of each of the interconnected devices in an effort toreduce chip overall power consumption as well as improve devicelongevity and reduce the chance that cross-talk between adjacentlyconnected devices, which can alter a nonvolatile memory's device state.Therefore, it is desirable to form a nonvolatile memory device that haslow programming currents when switching the device between the “on” and“off” states.

The addition of individual current limiting resistors for each memoryelement can reduce the required programming currents. Thesecurrent-limiting resistors are typically formed by adding a second layerof a fixed resistive material adjacent to the bistable resistivematerial forming the memory elements, as is disclosed in co-owned U.S.patent application Ser. No. 13/353,000 entitled “Nonvolatile MemoryDevice Having A Current Limiting Element” filed on Jan. 18, 2012, whichclaims priority to U.S. Provisional Patent Application No. 61/513,355entitled “Nonvolatile Memory Device Having A Current Limiting Element,”filed on Jul. 29, 2011, both of which are incorporated herein byreference. This extra layer requires an additional process step.

SUMMARY OF THE INVENTION

Embodiments of the present invention include nonvolatile memory elementsand methods of preparing them. The nonvolatile memory elements comprisea first layer operable as a first electrode, and a second layer operableas a resistive switching layer. The second layer comprises a compoundcomprising Me¹ _(v)Me² _(w)Si_(x)O_(y)N_(z), where Me¹ and Me² aremetals, v≧0, w≧0, x≧0, y>0, and z≧0, and at least one of v, w, and x isgreater than zero, having near-stoichiometric composition and bistableresistance. The memory element further comprises a third layer, whereinthe third layer is operable as a second electrode. At least one of thefirst layer or the third layer is a resistive layer comprising asubstoichiometric nitride or substoichiometric oxynitride, and having aresistivity between 0.1 and 10 Ωcm. In some embodiments, the resistivelayer is in contact with the second layer. In some embodiments, both thefirst layer and the third layer are resistive layers. In someembodiments, the resistive layer is operable as a source of oxygenvacancies that can migrate into the second layer during the set cycle,and is operable as a sink for oxygen vacancies that can migrate out ofthe second layer during the reset cycle. In some embodiments, the secondlayer comprises a transition metal oxide or transition metal oxynitride.In some embodiments, the resistive layer comprises a transition metalnitride or transition metal oxynitride. The transition metal cancomprise hafnium, tantalum, zirconium, lanthanum, niobium, or tungsten.The metals, Me¹ and Me², can each be selected from the group consistingof tantalum, niobium, hafnium, yttrium, zirconium, lanthanum, vanadium,titanium, tungsten, nickel, and aluminum.

Novel fabrication methods for the nonvolatile memory elements and theresistive electrodes are also disclosed. The resistive layers comprisinga substoichiometric nitride or substoichiometric oxynitride can beformed by reactive sputtering in an atmosphere comprising nitrogen or acombination of nitrogen and oxygen. Typically, the atmosphere has atotal pressure between about 1 and about 5 mTorr. In some embodiments,the atmosphere has a total pressure between about 10 and about 50 mTorr.In some embodiments, the substoichiometric nitride or substoichiometricoxynitride is formed by reactive sputtering wherein the sputtered atomsimpinge on the growing second electrode layer at an incident anglegreater than about 55 degrees relative to the surface normal. In someembodiments, the substoichiometric nitride or substoichiometricoxynitride is formed by reactive sputtering wherein a substrate biasvoltage is set substantially higher than a bias voltage at which aminimum resistivity occurs in the substoichiometric transition metalnitride or substoichiometric oxynitride. The second layer comprises atransition metal oxide or transition metal oxynitride. The transitionmetal comprises hafnium, tantalum, zirconium, lanthanum, niobium, ortungsten. Me¹ and Me² can each be selected from the group consisting oftantalum, niobium, hafnium, yttrium, zirconium, lanthanum, vanadium,titanium, tungsten, nickel, and aluminum. The resistive layer comprisesa transition metal nitride or transition metal oxynitride. Processcontrol for reactive sputtering of the second electrode layer can beimproved by using increased carrier gas pressure, detuning the substratebias, or using an oblique incident angle for the metal atoms.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a diagram of an illustrative array of resistive switchingnonvolatile memory elements.

FIG. 2A is a cross-sectional view of an illustrative resistive switchingnonvolatile memory element.

FIG. 2B is a cross-sectional view of an illustrative resistive switchingnonvolatile memory element.

FIG. 3 shows a graph illustrating how a resistive switching nonvolatilememory element of the types shown in FIGS. 2A and 2B may exhibitbistable behavior.

FIG. 4 is a schematic diagram of an illustrative resistive switchingnonvolatile memory element in series with a diode.

FIG. 5 is a schematic diagram of an illustrative resistive switchingmemory element in series with an electrical device.

FIG. 6 is a schematic diagram of an illustrative resistive switchingmemory element in series with two electrical devices.

FIG. 7 is a schematic circuit diagram of an illustrative resistiveswitching memory element showing an embedded current steering diode andcurrent limiting resistor.

FIG. 8 is a cross-sectional view of an illustrative resistive switchingnonvolatile memory element corresponding to the circuit of FIG. 7.

FIG. 9 is a cross-sectional view of an illustrative resistive switchingnonvolatile memory element, where the top conductor included thefunction of the embedded resistor.

FIG. 10 is a schematic diagram showing oxygen vacancy migration duringset and reset operations on a resistive switching memory layer.

FIG. 11 shows simulated data for resistivity as a function of sputteringchamber pressure.

FIG. 12 shows simulated data for resistivity as a function of sputteringchamber substrate bias voltage.

FIG. 13 shows sputtering at an oblique angle.

FIG. 14 shows simulated data for resistivity as a function of sputteringangle.

DETAILED DESCRIPTION

Before the present invention is described in detail, it is to beunderstood that unless otherwise indicated this invention is not limitedto specific resistive switching layer compositions. Exemplaryembodiments will be described for a plurality of layers comprisingTa₂O_(5-δ) (near stoichiometric, bistable resistance) layers andTaO_(2.5-x), (substoichiometric, resistive) layers, but bilayers andmultilayers comprising stoichiometric, near-stoichiometric, andsubstoichiometric oxides, nitrides, and oxynitrides of any metal orsilicon can beneficially be produced using the methods disclosed herein.It is also to be understood that the terminology used herein is for thepurpose of describing particular embodiments only and is not intended tolimit the scope of the present invention.

It must be noted that as used herein and in the claims, the singularforms “a,” “and” and “the” include plural referents unless the contextclearly dictates otherwise. Thus, for example, reference to “a layer”includes two or more layers, and so forth.

Where a range of values is provided, it is understood that eachintervening value, to the tenth of the unit of the lower limit unlessthe context clearly dictates otherwise, between the upper and lowerlimit of that range, and any other stated or intervening value in thatstated range, is encompassed within the invention. The upper and lowerlimits of these smaller ranges may independently be included in thesmaller ranges, and are also encompassed within the invention, subjectto any specifically excluded limit in the stated range. Where the statedrange includes one or both of the limits, ranges excluding either orboth of those included limits are also included in the invention. Wherethe modifier “about” is used, the stated quantity may vary by ±10%.Where the modifier “substantially higher” is used, the larger quantityis understood to be at least 20% larger in value than the smallerquantity.

DEFINITIONS

As used herein, the term “near-stoichiometric” refers to compounds wherethe atomic ratio deviates only slightly from the stoichiometricallycorrect ratio (wherein valence electrons are all balanced). Fornear-stoichiometric metal oxides described herein, there is typically aslight deficit of oxygen atoms relative to that of the fully oxidizedmetal, that deficit being sufficient to create defects in the latticeand a bistable resistance characteristic in sufficiently thin layers.For notational convenience, such near-stoichiometric oxides areabbreviated by adding a “−δ” after the number of oxygen atoms in anotherwise stoichiometric formula (e.g., Ta₂O_(5-δ)). Much as withsemiconductor doping, very small concentrations (<0.01%) of “defects” inthe form of missing 0 atoms can be sufficient to create thin layers withbistable resistance. (Many authors use Ta₂O_(5-x), instead ofTa₂O_(5-δ); δ is used in lieu of x herein to help clarify whether anear-stoichiometric or substoichiometric oxide is meant.) Thesenear-stoichiometric layers provide the resistive switching functionalityof the resistive switching nonvolatile memory elements described herein.

As used herein, the term “substoichiometric” refers to compounds wherethe atomic ratio deviates significantly (more than 0.01%) from thestoichiometrically correct ratio. For substoichiometric oxides describedherein, there is a larger deficit of oxygen atoms (compared tonear-stoichiometric oxides) sufficient to create continuous permanentstrings of defects in the lattice and a linear resistancecharacteristic. For notational convenience, such oxides are abbreviatedby adding a “−x” after the relative number of oxygen atoms in a formulawhere the count of metal atoms is taken to be 1 (e.g., TaO_(2.5-x)).Substoichiometric nitrides exhibit resistive behavior in comparison withtheir base metals.

As used herein, the term “conductor” refers to a volume of material(such as a wire, thin layer, or electrode) comprising a “conductivematerial.” The material is said to be “conductive” if there isnegligible voltage drop across the conductor at operating currents. Incertain instances, a small voltage drop is acceptable, althoughtypically the voltage drop across adjacent components is much larger.

Embodiments of the present invention include nonvolatile memory elementsthat can be formed without the need for a separate current-limitingresistor layer and process step by combining the functionality of acurrent-limiting resistor with one of the electrodes of a nonvolatilememory element. Accordingly, embodiments of the present invention relateto nonvolatile memory formed from resistive switching memory elements.Embodiments of the invention also relate to fabrication methods that maybe used to form nonvolatile memory having resistive switching memoryelements.

Resistive switching elements may be formed on any suitable type ofintegrated circuit. Most typically, resistive switching memory elementsmay be formed as part of a high-capacity nonvolatile memory integratedcircuit. Nonvolatile memory integrated circuits are often used as datastorage devices in portable and non-portable computing machines as wellas portable devices such as digital cameras, mobile telephones, handheldcomputers, vehicles, appliances, and music players. Nonvolatile memorydevices are packaged in memory cards or memory keys that can beremovably installed in electronic equipment by a user.

The use of resistive switching memory elements to form memory arrays onmemory devices is merely illustrative. In general, any suitableintegrated circuit may be formed using the resistive switchingstructures of the present invention. Fabrication of memory arrays formedof resistive switching memory elements is described herein as anexample.

Memory arrays formed of resistive switching memory elements are known as“resistive random access memory” or “ReRAM.” In certain embodiments, thefirst electrodes of each nonvolatile memory element are coplanar andarranged as a first set of parallel electrodes, and the secondelectrodes of each nonvolatile memory element are coplanar and arrangedas a second set of parallel electrodes at an angle to the first set ofparallel electrodes.

An illustrative memory array 10 of resistive switching memory elements12 is shown in FIG. 1. Memory array 10 may be part of a memory device orother integrated circuit. Read and write circuitry is connected tomemory elements 12 using conductors 16 and orthogonal conductors 18.Conductors such as conductors 16 and conductors 18 are sometimesreferred to as word lines and bit lines and are used to read and writedata into the elements 12 of array 10. Individual memory element 12 orgroups of memory elements 12 can be addressed using appropriate sets ofconductors 16 and 18. Memory element 12 may be formed from one or morelayers of materials, as indicated schematically by lines 14 in FIG. 1.In addition, the memory arrays shown can be stacked in a verticalfashion to make multi-layer 3-D memory arrays.

During a read operation, the state of a memory element 12 can be sensedby applying a sensing voltage to an appropriate set of conductors 16 and18. Depending on its history, a memory element that is addressed in thisway may be in either a high resistance state or a low resistance state.The resistance of the memory element therefore determines what digitaldata is being stored by the memory element. If the memory element has ahigh resistance, for example, the memory element may be said to containa logic one (i.e., a “1” bit). If, on the other hand, the memory elementhas a low resistance, the memory element may be said to contain a logiczero (i.e., a “0” bit). During a write operation, the state of a memoryelement can be changed by application of suitable write signals to anappropriate set of conductors 16 and 18.

A cross-section of an illustrative embodiment of a resistive switchingmemory element is shown in FIG. 2A. In the example of FIG. 2A, memoryelement 12 (as shown in FIG. 1) is formed from a metal oxide memorylayer 22 and has conductive electrodes 20 and 24. When constructed aspart of an array such as array 10 of FIG. 1, conductive lines such aslines 16 and 18 may be physically and electrically connected toelectrodes 20 and 24. Such conductive lines may be formed from anysuitable metals (e.g., tungsten, aluminum, copper, metal silicides,etc.). Conductive lines 16 and 18 may also be formed from otherconductive materials (e.g., doped polysilicon, doped silicon, etc.),combinations of these materials, or any other suitable conductivematerial. If desired, conductive line 16 and conductive line 18 mayserve as both conductive lines and as electrodes. In this type ofarrangement, line 16 may serve as electrode 20, so that no separateconductor is needed to form an upper electrode for element 12.Similarly, line 18 may serve as electrode 24, so that no separateconductor is needed for the lower electrode of element 12.

In the diagram of FIG. 2A, conductive lines 16 and 18 are shownschematically as being formed in contact with electrodes 20 and 24.Other arrangements may be used if desired. For example, there may beintervening electrical components (e.g., resistors, diodes, transistors,etc.) that are formed between line 16 and electrode 20 or between line18 and electrode 24.

If desired, there may be an intervening electrical component between anelectrode and resistive switching layer 22. An illustrative arrangementin which there is an intervening electrical component 38 betweenelectrode 24 and metal oxide 22 is shown in FIG. 2B.

As indicated schematically by dotted lines 21, conductive materials suchas electrodes 24 and 20 may be formed from one or more layers ofmaterials. Examples of materials that may be used to form electrodes 20and 24 include metal (e.g., refractory or transition metals), metalalloys, metal nitrides (e.g., refractory metal nitrides), metal siliconnitrides (i.e., materials containing refractory metals, transitionmetals, or other metals, along with silicon, and nitrogen), metalsilicides, or other conductors. A titanium nitride layer or similarbarrier layer under lower electrode 24 can be added to prevent metalsand other doping and alloying elements from diffusing into an underlyingsilicon structure.

Resistive switching memory element 12 exhibits a bistable resistance.When resistive switching memory element 12 is in a high resistancestate, it may be said to contain a logic one. When resistive switchingmemory element 12 is in a low resistance state, it may be said tocontain a logic zero. (If desired, high resistance can signify a logiczero and low resistance can signify a logic one.) The state of resistiveswitching memory element 12 may be sensed by application of a sensingvoltage. When it is desired to change the state of resistive switchingmemory element 12, read and write circuitry may apply suitable controlsignals across terminals 16 and 18.

A current (I) versus voltage (V) plot for memory element 12 is shown inFIG. 3. Initially, memory element 12 may be in a high resistance state(e.g., storing a logic one). In this state, the current versus voltagecharacteristic of memory element 12 is represented by solid line HRS 26.The high resistance state of memory element 12 can be sensed by read andwrite circuitry. For example, read and write circuitry may apply a readvoltage V_(read) to memory element 12 and can sense the resulting lowcurrent I_(L) that flows through memory element 12. When it is desiredto store a logic zero in memory element 12, memory element 12 can beplaced into its low-resistance state. This may be accomplished by usingread and write circuitry to apply a voltage V_(set) across terminals 16and 18 of memory element 12. Applying V_(set) to memory element 12causes memory element 12 to enter its low resistance state, as indicatedby dotted line 30. In this region, the structure of memory element 12 ischanged (e.g., through the formation of current filaments through memorylayer 22 or other suitable mechanisms), so that, following removal ofthe voltage V_(set), memory element 12 is characterized by lowresistance curve LRS 28.

The low resistance state of memory element 12 can be sensed using readand write circuitry. When a read voltage V_(read) is applied toresistive switching memory element 12, read and write circuitry willsense the relatively high current value I_(H), indicating that memoryelement 12 is in its low resistance state. When it is desired to store alogic one in memory element 12, the memory element can once again beplaced in its high resistance state by applying a voltage V_(reset) tomemory element 12. When read and write circuitry applies V_(reset) tomemory element 12, memory element 12 enters its high resistance stateHRS, as indicated by dotted line 32. When the voltage V_(reset) isremoved from memory element 12, memory element 12 will once again becharacterized by high resistance line HRS 26. Typical values of V_(set)and V_(reset) can be in the range 1-4 V, and V_(read) can be about 0.5V.

The bistable resistance of resistive switching memory element 12 makesmemory element 12 suitable for storing digital data. Because no changestake place in the stored data in the absence of application of thevoltages V_(set) and V_(reset), memory formed from elements such asmemory element 12 is nonvolatile.

Any suitable read and write circuitry and array layout scheme may beused to construct a nonvolatile memory device from resistive switchingmemory elements such as memory element 12. For example, horizontal andvertical lines 16 and 18 may be connected directly to the terminals ofresistive switching memory elements 12. This is merely illustrative. Ifdesired, other electrical devices may be associated with each memoryelement 12.

An example is shown in FIG. 4. As shown in FIG. 4, a diode 36 may beplaced in series with resistive switching memory element 12. Diode 36may be a Schottky diode, a p-n diode, a p-i-n diode, or any othersuitable diode.

If desired, other electrical components can be formed in series withresistive switching memory element 12. As shown in FIG. 5, electricaldevice 38 may be placed in series with resistive switching memoryelement 12. Device 38 may be a resistor, a diode, a transistor, or anyother suitable electronic device. Because devices such as these canrectify or otherwise alter current flow, these devices are sometimesreferred to as rectifying elements or current steering elements. Asshown in FIG. 6, two electrical devices 38 may be placed in series witha resistive switching memory element 12.

Memory elements 12 may be formed in a single layer in array 10 or may beformed in multiple layers. An advantage of forming memory arrays such asmemory array 10 of FIG. 1 using a multi-layer memory element scheme isthat this type of approach allows memory element density to bemaximized.

If desired, a resistive switching metal oxide layer may be formed aboveor below a diode (as an example). Conductive lines 16 and 18 may beelectrically coupled to metal oxide layer 22 through a number of layersof conductive material. There may, in general, be any suitable number ofconductive layers associated with resistive switching memory element 12.These conductive layers may be used for functions such as adhesionpromotion, seed layers for subsequent electrochemical deposition,diffusion barriers to prevent undesired materials from diffusing intoadjacent structures, contact materials (e.g., metals, metal alloys,metal nitrides, etc.) for forming ohmic contacts with the metal oxide22, contact materials (e.g., metals, metal alloys, metal nitrides, etc.)for forming Schottky contacts to the metal oxide 22, etc.

The conductive layers in memory element 12 may be formed from the sameconductive material or different conductive materials. Moreover,conductive layers in memory element 12 may be formed using the sametechniques or different techniques. As an example, one layer of aconductor may be formed using physical vapor deposition (PVD) techniques(e.g., sputter deposition), whereas another layer of a conductor may beformed using electrochemical deposition.

The portions of the conductive layers in memory element 12 that areimmediately adjacent to metal oxide 22 or are otherwise in closeassociation with metal oxide 22 are sometimes referred to as theelectrodes of the resistive switching memory element 12.

In general, the electrodes of resistive switching memory element 12 mayeach include a single material (e.g., tantalum), may each includemultiple materials (e.g., tantalum and titanium nitride), may includematerials formed using different techniques (e.g., electrochemicallydeposited tantalum and PVD tantalum), or may include combinations ofsuch materials.

Certain metal oxides are particularly appropriate for forming theresistive switching metal oxide layer 22. These metal oxides mayinclude, for example, the transition metal oxides and mixtures thereof.In a preferred embodiment, tantalum oxide is used in forming theresistive switching metal oxide layer. In certain other embodiments,oxides and oxynitrides of tantalum, niobium, hafnium, yttrium,zirconium, lanthanum, vanadium, titanium, tungsten, nickel, aluminum,and silicon and combinations thereof can be used in forming theresistive switching metal oxide layer.

Any suitable conductive materials may be used for forming the electrodes20 and 24 of resistive switching memory element 12. Illustrativeconductive materials include transition metals (and their nitrides andoxynitrides), refractory metals (and their nitrides and oxynitrides),and noble metals. Illustrative examples of conductive materials includeTi, Ta, W, Mo, Hf, Nb, Ni, Pd, Pt, Re, Ru, and Ir. Illustrative metalnitrides include titanium nitride, tantalum nitride, niobium nitride,hafnium nitride tungsten nitride, and molybdenum nitride. These aremerely illustrative examples of materials that may be used forelectrodes 20 and 24. Combinations of two or more of these materialsmetals (and/or their nitrides and/or oxynitrides) may be used or othersuitable conductive materials may be used as electrodes 20 and 24, ifdesired.

At least one electrode 20 or 24 is a resistive electrode. In preferredembodiments, whichever electrode is adjacent to the resistive switchingmemory element 12 has a suitable resistivity as discussed in detailbelow. In certain embodiments, both electrodes can be resistiveelectrodes.

The electrodes 20 and 24 and other conductive layers that may beassociated with memory element 12 may be formed using any suitabletechniques. Illustrative conductive material fabrication techniquesinclude physical vapor deposition (e.g., sputter deposition,evaporation), chemical vapor deposition, atomic layer deposition, andelectrochemical deposition (e.g., electroless deposition,electroplating).

One useful device that can be added to a nonvolatile memory element is acurrent limiting resistor 71 as illustrated in FIG. 7. Also shown inFIG. 7 is a steering diode 36, although current limiting resistors canalso be useful in memory architectures not requiring steering elements.These individual current limiting resistors can reduce the currentrequired to set and reset the state of the resistive switching memorylayer 22. Typically, the current limiting resistor is formed as aseparate layer within a complete nonvolatile memory element stack asshown in FIG. 8. However, the present inventors have discovered that itis advantageous to combine the function of one electrode with theresistor function into a single layer as shown in FIG. 9, where thecurrent limiting resistor 71 and top electrode 24 from FIG. 8 have beencombined into a single resistive layer 91. References herein to a “top”or “bottom” electrode are solely for convenience and imply nothing withrespect to any device orientation or the order of deposition of layers.

The set and reset operations involve breaking and reforming theconductive filaments in the resistive switching memory layer. When usingmetal oxides to form the memory layer, the conductive filaments compriseconnected strings of oxygen vacancies within a thin oxide layer. Inorder to break and reform these filaments, oxygen vacancies mustmigrate. Adjacent material layers such as electrodes and resistors canprovide a source and sink for these oxygen vacancies. It is advantageousto select materials for these adjacent layers that allow such migrationto occur with minimum applied power (voltage and current). With theright choice of materials, the top electrode 91 in FIG. 9 can providethis additional function so that top electrode 91 is simultaneously (1)an electrode, (2) a current limiting resistor, and (3) a source and sinkfor oxygen vacancies. Therefore, in a preferred embodiment, theresistive layer is in contact with the memory layer.

FIG. 10 shows schematically how oxygen vacancies can migrate in and outof a metal oxide memory layer as voltages are cycled. When V_(set) isapplied, oxygen vacancies are drawn from the top electrode into thememory layer, and when V_(reset) is applied, the oxygen vacancies returnto the top electrode. The “device” layer shown could represent asteering diode which is not a good source or sink of oxygen vacancies.

The material requirements for a multifunction electrode depend on thedesign architecture of a specific memory array. For example, consider a43 nm square (area A=43² nm²) memory element with a 100 Å (length L=10nm) thick top electrode. A typical target resistance for the currentlimiting function is R=100-200 kΩ. The required resistivity is given byτ=R(A/L)=R(43²/10)=18,490-36,980 Ωnm≅=1.8-3.7 Ωcm. To provide for gooddesign latitude and accommodate newer fabs with line widths down toabout 10 nm, this range can be expanded; generally, it is desired to beable to tune the resistivity of a top electrode material in the range0.1-10 Ωcm.

In accordance with one or more embodiments of the present invention, anonvolatile memory element comprises a resistive switching memory layerhaving bistable resistance formed between a first electrode layer and asecond electrode layer, with an optional steering element such as ap-i-n diode between one electrode layer and the memory layer. Thenonvolatile memory element comprises a first layer operable as a firstelectrode, and a second layer operable as a resistive switching layer.The second layer comprises a compound comprising Me¹ _(v)Me²_(w)Si_(x)O_(y)N_(z), where Me¹ and Me² are metals, v≧0, w≧0, x≧0, y>0,and z≧0, and at least one of v, w, and x is greater than zero, havingnear-stoichiometric composition and bistable resistance. In someembodiments, the second layer comprises a transition metal oxide ortransition metal oxynitride. The memory element further comprises athird layer, wherein the third layer is operable as a second electrode.At least one of the first layer or the third layer is a resistive layercomprising a substoichiometric nitride or substoichiometric oxynitride,and having a resistivity between 0.1 and 10 Ωcm. In some embodiments,the resistive layer comprises a transition metal nitride or transitionmetal oxynitride. The transition metals can comprise hafnium, tantalum,zirconium, lanthanum, niobium, or tungsten. The metals, Me¹ and Me², caneach be selected from the group consisting of tantalum, niobium,hafnium, yttrium, zirconium, lanthanum, vanadium, titanium, tungsten,nickel, and aluminum.

In some embodiments, the resistive layer is in contact with the secondlayer. In some embodiments, both the first layer and the third layer areresistive layers. In some embodiments, the resistive layer is operableas a source of oxygen vacancies that can migrate into the second layerduring the set cycle, and is operable as a sink for oxygen vacanciesthat can migrate out of the second layer during the reset cycle.

Many electrode materials can be used as described above. For example, aconductive electrode layer can be formed from a doped polycrystallinesilicon layer, and another conductive or resistive electrode layer canbe formed from a metal nitride. Metal nitride layers are frequentlychosen for electrodes, because they are stable, have good conductivity,are easy and inexpensive to form. TiN is a common choice, partly becauseit is a particularly good conductor. For the present purposes, wheresome resistivity is desired, other transition metal nitrides, forexample, nitrides of tantalum, hafnium, and niobium can be moresuitable.

In some embodiments, ReRAM devices comprising an array of nonvolatilememory elements can be prepared. The first electrode layers of eachnonvolatile memory element are coplanar and arranged as a first set ofparallel electrodes, and the second electrode layers of each nonvolatilememory element are coplanar and arranged as a second set of parallelelectrodes at an angle to the first set of parallel electrodes.

Methods of Forming Resistive Nitrides

In certain embodiments, methods of forming a nonvolatile memory elementcomprise forming a first layer, operable as a first electrode, andforming a second layer, operable as a resistive memory layer andcomprising a near-stoichiometric metal oxide having bistable resistance.The methods further comprise forming a third layer, operable as a secondelectrode. The memory layer is disposed between the first and secondelectrode layers. At least one of the electrode layers is a resistivelayer comprising a sub-stoichiometric transition metal nitride oroxynitride, having a resistivity between 0.1 and 10 Ωcm. Both the firstand third layers can be resistive layers. Preferably, the resistivelayer is in contact with the memory layer. The second layer comprises acompound comprising Me¹ _(v)Me² _(w)Si_(x)O_(y)N_(z), where Me¹ and Me²are metals, v≧0, w≧0, x≧0, y>0, and z≧0, and at least one of v, w, and xis greater than zero, having near-stoichiometric composition andbistable resistance. In some embodiments, the resistive layer comprisesa transition metal nitride or transition metal oxynitride. Thetransition metals can comprise hafnium, tantalum, zirconium, lanthanum,niobium, or tungsten. The metals, Me¹ and Me², can each be selected fromthe group consisting of tantalum, niobium, hafnium, yttrium, zirconium,lanthanum, vanadium, titanium, tungsten, nickel, and aluminum.

The substoichiometric nitride or substoichiometric oxynitride can beformed by reactive sputtering in an atmosphere comprising nitrogen or acombination of nitrogen and oxygen. In order to form nitride layers withwell-controlled resistivity, it is desirable to operate in a parameterspace where the resistivity changes slowly with one or more processparameters. In some cases, commonly used ranges of process parametersfail to provide the required level of control, because the resistivityof layers is too steep a function of the available process parameters.Alternate approaches can be helpful to provide process parameters suchthat the resistivity of layers can be well-controlled. Three methods areprovided that can improve process control parameters for reactivesputtering of metal nitride layers.

According to the first method, the pressure in the sputtering chamber isincreased significantly from the normal operating point. In someembodiments, the atmosphere has a total pressure between about 10 andabout 50 mTorr. Typically, to form a metal nitride using dc reactivesputtering, an Ar/N₂ atmosphere at 1-5 mTorr is used. The nitrogencontent of the formed layer can be varied by varying the N₂concentration in the Ar/N₂ atmosphere. The resulting layer resistivityis shown qualitatively in FIG. 11, where the “Low Pressure” curvecorresponds roughly to typical operating conditions. (Data shown aresimulations and do not represent real data for any particular metalnitride, sputtering power, or any particular operating pressure.) Forthe “Low Pressure” curve, the resistivity in the target range of 0.1-10Ωcm is a steep function of the nitrogen flow rate in a range C1-C2, andaccurate control of resistivity would be very difficult. However, thecurves shift and flatten with increasing pressure, and the usefulcontrol range broadens to B1-B2 at “Medium Pressure” and further toA1-A2 at “High Pressure.” Exemplary pressures suitable for the higheroperating pressures are in the range 10-50 mTorr.

According to the second method, the substrate bias applied duringsputtering is adjusted in an abnormal way. In some embodiments, thesubstoichiometric nitride or substoichiometric oxynitride can be formedby reactive sputtering wherein a substrate bias voltage is setsubstantially higher (more than 20%) than the bias voltage at which aminimum resistivity occurs in the substoichiometric transition metalnitride or substoichiometric oxynitride. A typical (simulation) exampleof how nitride layer resistivity varies with substrate bias is shown inFIG. 12. In normal operation, the substrate bias is selected to maximizelayer density through ion bombardment. Maximum layer density correlateswith minimum layer resistivity. The layer density (and thereforeresistivity) decreases to either side of this “optimum” substrate bias.In both directions, the defect density in the layer increases. Whilethere is a limit to the defect density that can be achieved at lowsubstrate bias, there is no such limit to the high side, and, inprinciple, arbitrary layer resistivity can be achieved. For example, inthe simulated example of FIG. 12, a useful process range is found forsubstrate biases between D1 and D2, both substantially above the bias atwhich resistivity is minimized. In practice, depending on other processparameters, the curve may become too steep in the target range, and thismethod can usefully be combined with the first and/or third methods tooptimize process control.

According to the third method, as shown in FIG. 13, the sputter gun ispositioned at an oblique angle. The typical position of the sputter gunis directly overhead at 90° from the substrate plane. In someembodiments, the substoichiometric nitride or substoichiometricoxynitride can be formed by reactive sputtering wherein the sputteredatoms impinge on the growing second electrode layer at an incident anglegreater than about 55° relative to the surface normal (e.g., from about55° to about 85° relative to the surface normal). As shown qualitativelyin FIG. 14, the reduced normal momentum from atoms incident at aglancing angle can also increase defect density and thereforeresistivity to provide an additional control parameter.

In order to tune the resistivity of a nitride, one can form asubstoichiometric composition where there is excess nitrogen in theformed layer. Depending on the particular metal used, the detailedcomposition of such a layer can vary. Most transition metals havemultiple possible valence states even if one predominates, and a mixtureof nitrides of different stoichiometry can be formed. For example, up toseven forms of tantalum nitride were found in layers formed by ion-beamassisted deposition (IBAD). In order of increasing nitrogen content,these were cubic β-TaN_(0.05), hexagonal γ-Ta₂N, hexagonal δ-TaN,hexagonal ε-TaN, hexagonal Ta₅N₆, tetragonal Ta₄N₅, and tetragonal Ta₃N₅(see, for example, Arranz & Palacio, “Composition of tantalum nitridethin films grown by low-energy nitrogen implantation: a factor analysisstudy of the Ta 4f XPS core level,” available online atarxiv.org/ftp/cond-mat/papers/0409/0409712.pdf).

As discussed in Example 1, tantalum nitride layers can be made byreactive sputtering in an Ar/N₂ atmosphere with varying concentrationsof N₂. Resistivities could be achieved in the range of interest (0.1-10Ωcm) using a nitrogen flow rates above about 50%. (All relativeconcentrations are by volume, set as a volume flow rate such as standardcubic centimeters per minute [sccm].) However, other researchers (e.g.,Nazon, J. et al., “Effects of processing parameters on the properties oftantalum nitride thin films deposited by reactive sputtering,” J. Alloysand Compounds, 464: 526-31, 2008) have reported bulk resistivities fortantalum nitride that cover the desired range. Nazon (FIG. 6 therein)found resistivities for sputtered layers with the desired range for N₂concentrations of about 4-8% for 90 W sputtering power and a constant Arpressure of 6.5 Pa (49 mTorr).

Hafnium nitride layers can also be made in the appropriate resistivityrange. Preliminary sputtering experiments at 100 W and 5 mTorr indicatedthat the desired resistivity range could be obtained for N₂concentrations in the range˜10-16%. Hafnium appears to have at least twostable nitrides, a conductive HfN and a much more resistive Hf₃N₄.

In accordance with one or more embodiments of the present invention, theresistivity of a compound comprising a metal and nitrogen can be furtherincreased by adding oxygen to form an oxynitride of variablestoichiometry. Metal oxides are typically poor conductors, while metalnitrides are typically good conductors. Oxynitrides can exhibitintermediate conductivity by providing limited electron conduction pathsthrough the nitride regions.

In accordance with some embodiments, the substoichiometric nitride orsubstoichiometric oxynitride can be formed using atomic layer depositionusing appropriate precursors and oxygen reactant gas concentration,nitrogen reactant gas concentration, and exposure times. In accordancewith some embodiments, the substoichiometric nitride orsubstoichiometric oxynitride can also be formed using chemical vapordeposition using appropriate precursors and oxygen-containing gasconcentration, nitrogen-containing gas concentration, and exposuretimes. Typical precursors include tetrakis(dimethylamino)hafnium as a Hfprecursor, pentakis(dimethylamino)tantalum as a Ta precursor, andtris(dimethylamino)silane) as a Si precursor.

EXAMPLE Example 1 Tantalum Nitride Resistivity for Layers Made byReactive Sputtering

Tantalum nitride, hafnium nitride, and tantalum silicon nitride layerswere prepared using either PVD (dc reactive sputtering at 200 W in a 5mTorr Ar/N₂ atmosphere with varying N₂ flow rates) or ALD (usingalternating pulses of a metal precursor and NH₃ at a substratetemperature of 200-260 C; metal precursors includedtetrakis(dimethylamino)hafnium as a Hf precursor,pentakis(dimethylamino)tantalum as a Ta precursor, andtris(dimethylamino)silane) as a Si precursor.

Samples of TaN produced by PVD with a nitrogen flow rate above about 50%generally had resistivities in the range of interest (0.1-10 Ωcm) as didthe TaSiN sample. HfN samples showed useful resistivities for nitrogenflow rates in the range 10-15%. The data suggest that the resistivelayers comprising a sub-stoichiometric nitride or sub-stoichiometricoxynitride having the desired current limiting resistivity for anyparticular device design can be prepared when using an appropriatechoice of process conditions.

It will be understood that the descriptions of one or more embodimentsof the present invention do not limit the various alternative, modifiedand equivalent embodiments which may be included within the spirit andscope of the present invention as defined by the appended claims.Furthermore, in the detailed description above, numerous specificdetails are set forth to provide an understanding of various embodimentsof the present invention. However, one or more embodiments of thepresent invention may be practiced without these specific details. Inother instances, well known methods, procedures, and components have notbeen described in detail so as not to unnecessarily obscure aspects ofthe present embodiments.

What is claimed is:
 1. A method, comprising: forming a first layer byreactive sputtering in an atmosphere containing a source of nitrogen;wherein process conditions during the reactive sputtering comprises oneof a pressure between about 10 and 50 mTorr, a substrate bias more than120% of a value expected to minimize resistivity, or a sputtering anglebetween about 55 and 85 degrees; and wherein the first layer comprises asub-stoichiometric metal nitride or a sub-stoichiometric metaloxynitride having a resistivity between about 0.1 and 10 ohm-cm.
 2. Themethod of claim 1, wherein the first layer is operable as one of asource of oxygen vacancies or a sink of oxygen vacancies.
 3. The methodof claim 1, wherein the first layer is operable as a source of oxygenvacancies or alternatively as a sink of oxygen vacancies, depending onthe nature of an electric field applied to the first layer.
 4. Themethod of claim 1, wherein the atmosphere comprises more than about 50vol % nitrogen.
 5. The method of claim 1, wherein the atmosphere furthercomprises a source of oxygen.
 6. The method of claim 1, wherein a metalof the sub-stoichiometric metal nitride or the sub-stoichiometric metaloxynitride is a transition metal.
 7. The method of claim 6, wherein thetransition metal comprises one of hafnium, tantalum, zirconium,lanthanum, niobium, or tungsten.
 8. The method of claim 1, wherein thefirst layer comprises two elements selected from the group consisting oftantalum, niobium, hafnium, yttrium, zirconium, lanthanum, vanadium,titanium, tungsten, nickel, and aluminum.
 9. The method of claim 1,wherein the first layer comprises a mixture of nitrides of differentstoichiometries.
 10. The method of claim 1, wherein the first layercomprises a mixture of nitrides of different crystalline structures. 11.The method of claim 1, wherein the first layer comprises at least one ofa cubic crystalline structure, a tetragonal crystalline structure, or ahexagonal crystalline structure.
 12. The method of claim 1, wherein thefirst layer comprises at least one of b-TaN_(0.05), g-Ta₂N, d-TaN,e-TaN, Ta₅N₆, Ta₄N₅, or Ta₃N₅.
 13. The method of claim 1, wherein achamber pressure during the reactive sputtering is about 5 mTorr; theatmosphere comprises between about 10 and 16 vol % nitrogen; and thefirst layer comprises at least one of HfN or Hf₃N₄.
 14. The method ofclaim 1, wherein the process conditions during the reactive sputteringcomprise both the substrate bias more than 120% of the value expected tominimize resistivity and the pressure between about 10 and 50 mTorr. 15.The method of claim 1, wherein the process conditions during thereactive sputtering comprise both the substrate bias more than 120% ofthe value expected to minimize resistivity and the sputtering anglebetween about 55 and 85 degrees.
 16. The method of claim 1, furthercomprising: forming a second layer over the first layer; and forming athird layer over the second layer by reactive sputtering in anatmosphere containing a source of nitrogen; wherein a process conditionduring the reactive sputtering comprises one of a pressure between about10 and 50 mTorr, a substrate bias more than 120% of a valuecorresponding to minimum resistivity, or a sputtering angle betweenabout 55 and 85 degrees; and wherein the third layer comprises asub-stoichiometric metal nitride or a sub-stoichiometric metaloxynitride having a resistivity between about 0.1 and 10 ohm-cm.
 17. Themethod of claim 16, wherein the second layer is in contact with at leastone of the first layer or the third layer.
 18. The method of claim 16,wherein the second layer donates oxygen vacancies to, or receives oxygenvacancies from, at least one of the second layer or the third layerunder an applied electric field.
 19. The method of claim 16, wherein thesecond layer is near-stoichiometric.
 20. The method of claim 16, whereinthe second layer has bistable resistance.